JP2015017242A - Vinyl chloride-based film for food packaging - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinyl chloride-based film for food packaging which has low leachability (safety), packaging suitability (flexibility), and good film appearance.SOLUTION: A food packaging film is formed by mixing into a vinyl chloride resin (A) a modified epoxidized vegetable oil (B) whose polymer content is 5-50 mass%, an ester-based compound (C) of an aliphatic dibasic acid having 10 or less carbon atoms, the compound (C) having a weight average molecular weight of 200-1,000, and a polyester compound (D) having a weight average molecular weight of 3,000-10,000. The mixed amount of a mixture of the components (B) and (C) is 30-50 pts.mass based on 100 pts.mass of the component (A), and the content of the component (B) in the mixture of the components (B) and (C) is 30-70 mass%. The mixed amount of the component (D) is 5-15 pts.mass based on 100 pts.mass of the component (A).

Description

  The present invention relates to a film excellent in low elution (safety), packaging suitability (flexibility) and film appearance.

  BACKGROUND ART Stretch films excellent in transparency, flexibility, and heat sealability are widely used in food packaging, particularly fresh food packaging for packaging meat, fresh fish, fruits and vegetables. As this type of film, a film made of a polyvinyl chloride resin composition in which an adipate ester plasticizer and various antifogging agents are blended with a polyvinyl chloride resin is generally used.

  For food packaging films, the hygiene of compounding ingredients and the ability to migrate to food products are important. Therefore, FDA standards (Food and Drug Administration) in the US and PL standards (vinyl chloride resin packaging containers in Japan) Self-regulation standards for packaging, etc.) are established, and resins, additives, etc. that meet these standards are used in food packaging films. In addition, as a test for confirming the transferability of additives to foods and the like, an extraction test has been conducted as an evaporation residue test method by the Ministry of Health and Welfare Notification No. 20 test.

  In such a background, regarding a food packaging film mainly composed of polyvinyl chloride or a resin composition for producing the film, for example, in Patent Document 1, an aliphatic polybasic acid polyester is added to a polyvinyl chloride resin. A vinyl chloride resin composition for food packaging using a plasticizer and a glycerin ester which is an edible plasticizer is disclosed.

  In patent document 2, it is manufactured by hydrogen peroxide method with respect to 100 parts by mass of chlorine-containing resin such as polyvinyl chloride resin, has a peroxide value of 13 or less, and does not contain a specific phosphorus antioxidant. A food packaging material comprising 1 to 50 parts by mass of epoxidized soybean oil is disclosed.

  In Patent Document 3, a specific adipic acid ester plasticizer is 15 to 45 parts by mass, an epoxidized vegetable oil is 1 to 30 parts by mass or less, and an average molecular weight is 1000 to 3000 with respect to 100 parts by mass of a polyvinyl chloride resin. The stretch film formed by blending a polyester-based plasticizer of 11 to 40 parts by mass and a higher fatty acid having 8 to 22 carbon atoms in a proportion of 0.1 to 1.0 parts by mass is disclosed.

  Patent Document 4 describes an aliphatic polybasic acid polyester plasticizer and an aliphatic polybasic ester plasticizer having a weight average molecular weight of 800 to 3,000 with respect to 100 parts by mass of a polyvinyl chloride resin. 17-21 parts by mass of a combination product (of which the ratio of the aliphatic polybasic polyester plasticizer is 20-40% by mass), 3-9 parts by mass of epoxidized vegetable oil, and a glycerin ester compound as an antifogging agent Is disclosed in a proportion of 0.5 to 3.0 parts by mass.

  As described above, a plasticizer is added to a food packaging film mainly composed of polyvinyl chloride in order to increase flexibility, but among wrapping films, a wrap film for food packaging is particularly sophisticated. Since flexibility is required, for example, the amount of plasticizer added to the extent disclosed in Patent Document 4 may be insufficient. On the other hand, when the addition amount of the plasticizer is increased, the elution amount of the plasticizer is increased, and it is not easy to achieve both.

  In the technique disclosed in Patent Document 3, a polyester plasticizer having an average molecular weight of 1000 to 3000 is a relatively easy elution plasticizer, so that a practically sufficient level of elution (safety) is ensured. There are cases where it is impossible

  In addition, in the technology disclosed in Patent Document 1, a sufficient plasticizing effect cannot be obtained only with an aliphatic polybasic polyester plasticizer, and when a large amount of glycerin ester is added, the amount of elution increases. Therefore, it is difficult to achieve both flexibility and low elution. In addition, for example, epoxidized soybean oil as disclosed in Patent Document 2 is a plasticizer derived from natural products, and is particularly suitable for food packaging applications. In addition to being easy to do, it may cause poor appearance of the film during storage.

  When a film to which a large amount of epoxidized soybean oil is added is stored at a low temperature, the soybean oil that bleeds out on the film surface solidifies, so that the film surface may be whitened and the appearance may be impaired. In addition, when a film containing a large amount of epoxidized soybean oil is stored under high temperature and high humidity, the bleed-out epoxidized soybean oil reacts with water to increase the molecular weight, resulting in a whitened film surface and an appearance. It may be damaged. Thus, in the technique disclosed in Patent Document 2, it is difficult not only to achieve both flexibility and low elution, but also to provide a food packaging film having an excellent appearance. is there.

  Thus, food packaging films often require not only low elution (safety) and packaging suitability (flexibility) but also good film appearance. These low elution, packaging suitability, and film appearance It is difficult to satisfy all of the above, and improvement is eagerly desired.

JP-A-2-269145 JP-A-8-27341 JP-A-9-176424 JP 2011-153210 A

  The present invention has been made in view of the above circumstances, and a solution to the problem is a vinyl chloride food packaging film that combines low elution (safety), packaging suitability (flexibility), and good film appearance. Is to provide.

  As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be easily solved by adopting a specific configuration, and the present invention has been completed.

  That is, the gist of the present invention is a modified epoxidized vegetable oil (B) having a multimer content of 5 to 50% by mass relative to the vinyl chloride resin (A), and a weight average molecular weight of 200 to 1000. An aliphatic dibasic ester compound (C) having 10 or less carbon atoms and a polyester compound (D) having a weight average molecular weight of 3000 to 10,000 are blended, and (A) (B) with respect to 100 parts by mass. And the blending amount of the mixture of (C) is 30 to 50 parts by mass, and the ratio of (B) in the mixture of (B) and (C) is 30 to 70% by mass, and (A ) It exists in the film for food packaging characterized by the compounding quantity of (D) with respect to 100 mass parts being 5-15 mass parts.

  The vinyl chloride food packaging film of the present invention uses the modified epoxidized vegetable oil (B) as a plasticizer, and is used for isooctane measured by the evaporation residue test method (single-sided method) stipulated in Ministry of Health and Welfare Notification No. 20 in 1982. Aliphatic dibasic acid ester compound (C) having a carbon number of 10 or less and a modified epoxy having a weight average molecular weight of 200 to 1000 and not only having a very low elution amount and excellent safety. The modified epoxidized vegetable oil (B) bleed out on the film surface is dissolved in the aliphatic dibasic acid ester compound (C) having 10 or less carbon atoms by mixing with the modified vegetable oil (B) at a specific ratio. Therefore, it is possible to produce a food packaging film that does not cause whitening of the film surface even at low temperature or high temperature and high humidity storage and has an excellent appearance. Yellow, it can be widely used as a wrap film for food packaging.

  Hereinafter, a food packaging film as an example of an embodiment of the present invention will be described. However, the scope of the present invention is not limited to the embodiments described below.

  As the vinyl chloride resin (A) used in the present invention, a vinyl chloride resin having an arbitrary average degree of polymerization can be used. Preferably, the average degree of polymerization of the vinyl chloride resin (A) is 800 to 1400. If the average degree of polymerization is 800 or more, sufficient mechanical strength can be obtained. On the other hand, if the average degree of polymerization is 1400 or less, heat generation due to an increase in melt viscosity does not occur, and coloring due to decomposition can be eliminated.

  Therefore, from such a viewpoint, the average degree of polymerization of the vinyl chloride resin (A) is more preferably 900 or more or 1350 or less in the above-mentioned range, and more preferably 1000 or more and 1300 or less. Is more preferable.

  As the vinyl chloride resin (A), in addition to a homopolymer of vinyl chloride (referred to as “vinyl chloride homopolymer”), a copolymer with a monomer copolymerizable with vinyl chloride (hereinafter, “ And a graft copolymer obtained by graft-copolymerizing vinyl chloride to a polymer other than this vinyl chloride copolymer (hereinafter referred to as vinyl chloride-based graft copolymer). Can do.

  In the vinyl chloride copolymer, the mechanical properties decrease when the content of constituent units other than vinyl chloride in the copolymer increases, so the proportion of vinyl chloride in the vinyl chloride copolymer is 60 to 99. It is preferable that it is mass%.

  The vinyl chloride homopolymer and the vinyl chloride copolymer can be polymerized by an arbitrary method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method and the like.

  Here, the monomer copolymerizable with vinyl chloride may be any monomer having a reactive double bond in the molecule. For example, α-olefins such as ethylene, propylene and butylene, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as butyl vinyl ether and cetyl vinyl ether; unsaturated carboxylic acids such as acrylic acid and methacrylic acid, methyl acrylate , Esters of acrylic acid or methacrylic acid such as ethyl methacrylate and phenyl methacrylate, aromatic vinyls such as styrene and α-methylstyrene, vinyl halides such as vinylidene chloride and vinyl fluoride, N-phenylmaleimide, N-substituted maleimides such as N-cyclohexylmaleimide can be used, and these can be used alone or in combination of two or more.

  As the polymer other than the vinyl chloride copolymer, any polymer capable of graft copolymerization with vinyl chloride may be used. For example, ethylene / vinyl acetate copolymer, ethylene / vinyl acetate / carbon monoxide copolymer, ethylene / ethyl acrylate copolymer, ethylene / ethyl acrylate / carbon monoxide copolymer, ethylene / methyl methacrylate copolymer, ethylene -A propylene copolymer, an acrylonitrile butadiene copolymer, a polyurethane, chlorinated polyethylene, a chlorinated polypropylene etc. can be mentioned, These can be used individually or in combination of 2 or more types.

  The modified epoxidized vegetable oil (B) used in the present invention is obtained by multiplying a part of the epoxidized vegetable oil. For example, the reaction product of the epoxidized vegetable oil and the carboxylic acid, and the peroxide value is 13.1. An example is one in which 18.0 milliequivalents (mEq) / kg of epoxidized vegetable oil is increased in quantity during melt kneading. Examples of the epoxidized vegetable oil include epoxidized soybean oil, epoxidized linseed oil, epoxidized cottonseed oil, epoxidized peanut oil, epoxidized safflower oil, epoxidized grape seed oil, and epoxidized olive oil. These can be used alone or as a mixture of two or more. Among these, epoxidized soybean oil and epoxidized linseed oil are preferably used from the viewpoint of compatibility with a vinyl chloride resin.

  In the modified epoxidized vegetable oil (B), the proportion of the multimer of the epoxidized vegetable oil in the modified epoxidized vegetable oil (B) is 5 to 50% by mass (in this case, the proportion of the monomer is 95 to 50% by mass). There must be. If the ratio of the multimer is 5 to 50% by mass, it is possible to achieve both plasticization and low elution property of the vinyl chloride resin. If the proportion of the multimer is 50% by mass or less, plasticization of the vinyl chloride resin is sufficient and excellent flexibility can be obtained. On the other hand, if the proportion of the multimer is 5% by mass or more, the plasticity Elution of the modified epoxidized vegetable oil (B) added as an agent can be sufficiently suppressed. A multimer refers to a dimer or more.

  From such a viewpoint, the range of the multimer in the modified epoxidized vegetable oil is 9% by mass or more (in this case, the monomer ratio is 91% by mass or less) or 40% by mass or less (in this case). The monomer ratio is preferably 60% by mass or more, and among them, 10% by mass or more (in this case, the monomer ratio is 90% by mass or less) or 35% by mass or less (in this case, simply It is more preferable that the proportion of the monomer is 65% by mass or more, and among them, 11% by mass or more (in this case, the proportion of the monomer is 89% by mass or less), or 30% by mass or less (in this case, the single amount) More preferably, the ratio of the body is 70% by mass or more.

The ratio of the epoxidized vegetable oil multimer in the modified epoxidized vegetable oil (B) can be measured by the following method. That is, using gel permeation chromatography (column: trade name TSKgel G2000HXL of Tosoh Corporation), THF as a solvent (solution concentration 2.5 mg / mL, solution injection amount 0.05 mL, flow rate 1 mL / min, temperature 40 ° C. ) Was used to measure. From the obtained chart, the proportion of the monomer of the epoxidized vegetable oil was calculated, and the proportion of the multimer was determined by the following formula.
Multimer ratio (mass%) = 100 (mass%) − “monomer ratio (mass%)”

  In addition, the measurement of the polymer of the epoxidized vegetable oil is performed by epoxidized vegetable oil itself, a product obtained by reacting epoxidized vegetable oil and carboxylic acid, vinyl chloride resin (A), components (B), (C) described later, You may measure in any step of what melt-kneaded (D) and the additive, and what formed the film.

  As a means for making the ratio of the polymer of the epoxidized vegetable oil in the modified epoxidized vegetable oil (B) 9 to 40% by mass, the epoxidized vegetable oil is reacted with a carboxylic acid to partly epoxidize the vegetable oil. A method of multimerizing, a method of increasing the amount of an epoxidized vegetable oil having a peroxide value of 13.1-18.0 milliequivalents (mEq) / kg at the time of melt kneading can be employed.

  As a method of reacting epoxidized vegetable oil and carboxylic acid, a method of polymerizing a mixture of epoxidized vegetable oil and carboxylic acid in advance at a temperature of 100 to 220 ° C. for about 10 minutes to 2 hours, for example. And vinyl chloride resin (A), polyester compound (C), epoxidized vegetable oil, carboxylic acid and other additives are all mixed and reacted in a kneader such as a mixer or an extruder to multimerize. Any method may be used, such as

  The carboxylic acid can react with an epoxidized vegetable oil such as epoxidized soybean oil to polymerize the epoxidized vegetable oil, and preferably the proportion of the multimer in the modified epoxidized vegetable oil is as described above. If it can be set to 5-40 mass%, it will not specifically limit. Examples of such carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, etc. Saturated carboxylic acids, oleic acid, linoleic acid, linolenic acid, sorbic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid and other unsaturated carboxylic acids, lactic acid, malic acid, citric acid and other hydroxy acids, benzoic acid, phthalic acid , Aromatic carboxylic acids such as isophthalic acid, terephthalic acid, salicylic acid, oxalic acid, malonic acid, dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, oxocarboxylic acid, aconitic acid, Carboxylic acid derivatives such as amino acids and nitrocarboxylic acids Gerare, singly or can be used as a mixture of two or more. Among these, it is preferable to use unsaturated carboxylic acid or dicarboxylic acid from the viewpoint of reactivity with epoxidized vegetable oil.

  The addition amount of the carboxylic acid is preferably 0.01 parts by mass or more and 8 parts by mass or less, and 0.05 parts by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the epoxidized vegetable oil. It is more preferable that it is 0.1 parts by mass or more and 3 parts by mass or less. By adding a carboxylic acid within such a range to the epoxidized vegetable oil, a modified epoxidized vegetable oil excellent in heat stability and flexibility imparted to the vinyl chloride resin and low elution can be obtained.

  On the other hand, when an epoxidized vegetable oil having a peroxide value of 13.1 to 18.0 milliequivalents (mEq) / kg is increased during melt kneading, a more preferable range of the peroxide value is 13.3 to 17.5 mm. The equivalent range is 13.5 to 17.0 meq / kg. When the peroxide value of the epoxidized vegetable oil is below this range, the peroxy group in the epoxidized vegetable oil is small, and it is difficult to achieve sufficient multimerization at the time of melt kneading with the polyvinyl chloride resin (A). . On the other hand, when the peroxide value exceeds this range, for example, the odor when formed into a film is severe and it may be difficult to use as a food packaging material.

  The peroxide value of the epoxidized vegetable oil (B) is determined based on the standard oil analysis method (2.5.2 Peroxide value, standard oil analysis test method (I), Japan Oil Chemists' Society established, 2003 edition, Nippon Oil Corporation. Based on the acetic acid / isooctane method of Chemical Society), it was determined from the number of milliequivalents of iodine (milliequivalent / kg) per 1 kg of epoxidized vegetable oil released when potassium iodide was added to the epoxidized vegetable oil (B).

  In the present invention, a modified epoxidized vegetable oil (B) bleeded out on the film surface by blending an aliphatic dibasic acid ester compound (C) having a weight average molecular weight of 200 to 1000 and having 10 or less carbon atoms. Dissolves in the aliphatic dibasic acid ester compound (C), suppresses solidification during low-temperature storage and reaction with water during high-temperature and high-humidity storage, and provides a film for food packaging excellent in appearance be able to.

  If the weight average molecular weight of the aliphatic dibasic acid ester (C) is 200 or more, excessive bleeding out of the aliphatic dibasic acid ester (C) does not occur, which is preferable for safety. On the other hand, if the weight average molecular weight of the aliphatic dibasic acid ester (C) is 1000 or less, the modified epoxidized vegetable oil (B) bleed out on the film surface is dissolved, and a film excellent in appearance can be obtained. . From this viewpoint, the weight average molecular weight of the aliphatic dibasic acid ester (C) is preferably 300 to 800, more preferably 350 to 600.

  Specific examples of the aliphatic dibasic acid ester compound (C) include dimethyl adipate (DMA), dibutyl adipate (DBA), diisobutyl adipate (DIBA), di-2-ethylhexyl adipate (DOA), Diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-2-ethylhexyl azelate (DOZ), dimethyl sebacate (DMS), dibutyl sebacate (DBS), di-2-ethylhexyl sebacate (DOS), etc. Is mentioned.

  The polyester compound (D) used in the present invention has a weight average molecular weight of 3000 to 10,000. If the weight average molecular weight of the said polyester-type compound (D) is 3000 or more, the elution of the said polyester-type compound (D) can be suppressed and it is preferable on safety. On the other hand, if the weight average molecular weight is 10,000 or less, the compatibility with the vinyl chloride resin is good, elution of the polyester compound can be suppressed, and a sufficient plasticizing effect can be obtained.

  From this viewpoint, a more preferable range of the weight average molecular weight of the polyester compound (D) is 4000 to 9000, and a more preferable range is 5000 to 8000 or less.

  Specific examples of the polyester compound (D) include adipic acid ester compounds, sebacic acid ester compounds, succinic acid ester compounds, and polyester polyols. Among these, in terms of compatibility with the vinyl chloride resin (A), it is preferable to use an adipic acid ester compound, a polyester polyol, or a mixture thereof.

  As an adipic acid ester compound, for example, a reaction product of adipic acid and a dihydric alcohol can be used. In this case, the dihydric alcohol is not particularly limited, and for example, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and the like can be used alone, or Any of two or more types of dihydric alcohols may be used.

  On the other hand, specific examples of the adipic acid ester compound include, for example, poly (propylene glycol / adipic acid) ester, poly (1,3-butanediol / adipic acid) ester, poly (1,4-butanediol / adipic acid) ) Ester, poly (ethylene glycol / adipic acid) ester, poly (1,6-hexanediol / butanediol / adipic acid) ester, poly (butanediol / ethylene glycol / adipic acid) ester, poly (ethylene glycol / propylene glycol) / Butanediol / adipic acid) ester.

  Of these, poly (1,3-butanediol / adipic acid) ester or poly (1,4-butanediol / adipic acid) is particularly preferred in terms of compatibility with vinyl chloride resin (A) and low elution. It is preferable to use an ester or a mixture thereof.

  Examples of the polyester polyol include those obtained by polycondensation of an aliphatic dicarboxylic acid and / or an aromatic dicarboxylic acid and a dihydric alcohol. Examples of the aliphatic dicarboxylic acid include succinic acid, adipic acid, sebacic acid, glutaric acid, and azelaic acid. Examples of the aromatic dicarboxylic acid include isophthalic acid and terephthalic acid. Examples of dihydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentadiol, neopentyl glycol, 1, 4-dihydroxymethylcyclohexane and the like can be mentioned.

  Specific examples of polyester polyols include polyethylene adipate diol, polybutylene adipate diol, pohexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate diol And so on. Among these, polyneopentyl adipate diol is preferably used in terms of compatibility with the vinyl chloride resin (A) and low elution.

  The blended amount of the modified epoxidized vegetable oil (B) and the aliphatic dibasic ester compound (C) with respect to 100 parts by mass of the vinyl chloride resin (A) is 30 to 50 parts by mass, and the modified epoxy The ratio of the modified epoxidized vegetable oil (B) in the mixture of the modified vegetable oil (B) and the aliphatic dibasic acid ester compound (C) is 30 to 70% by mass. Moreover, the compounding quantity of the polyester-type compound (D) with respect to 100 mass parts of said vinyl chloride resin (A) is 5-15 mass parts. If the blending amount of the mixture of the modified epoxidized vegetable oil (B) and the aliphatic dibasic ester compound (C) with respect to the vinyl chloride resin (A) is within the above range, the (B) and (C ), An optimum flexibility can be imparted to the wrap film. Moreover, if the ratio of the modified epoxidized vegetable oil (B) in the mixture of the modified epoxidized vegetable oil (B) and the aliphatic dibasic acid ester compound (C) is within the above range, a low temperature or a high temperature Even when stored for a long time under humidity, both flexibility and low elution can be achieved without causing poor film appearance.

  The blending amount of the modified epoxidized vegetable oil (B) and the aliphatic dibasic acid ester compound (C) with respect to 100 parts by mass of the vinyl chloride resin (A) is a ratio of 33 parts by mass or more, or 47 parts by mass or less. Among them, it is particularly preferable that the ratio is 36 parts by mass or more, or 42 parts by mass or less. The ratio of the modified epoxidized vegetable oil (B) in the mixture of the modified epoxidized vegetable oil (B) and the aliphatic dibasic acid ester compound (C) is 35% by mass or more, or 65% by mass or less. It is preferable that the ratio is 40% by mass or more, or 60% by mass or less. The blending amount of the polyester compound (D) with respect to the vinyl chloride resin (A) is preferably 7 parts by mass or more, or 13 parts by mass or less, and more preferably 9 parts by mass or more. The ratio is more preferably 11 parts by mass or less.

  By blending the modified epoxidized vegetable oil (B), the aliphatic dibasic acid ester compound (C), and the polyester compound (D) within such a range, low elution (safety) and packaging suitability (flexible) Property), film unwinding property, and film wrapping film excellent in film appearance.

  In order to improve the thermal stability of the food packaging film of the present invention, it is preferable to add a Ca—Zn stabilizer. The Ca—Zn stabilizer is a mixture of a calcium fatty acid salt and a zinc fatty acid salt. Specific examples of fatty acids include behenic acid, stearic acid, lauric acid, oleic acid, palmitic acid, ricinoleic acid, benzoic acid and the like, and can be used in combination of two or more according to the purpose. It is preferable to use a stearate from the viewpoint of moldability. Moreover, it is preferable that the ratio of calcium and zinc is 1: 2 to 1: 3 by mass ratio. If the ratio of zinc is less than 2 relative to calcium, a redness peculiar to calcium salts will appear. On the other hand, if the ratio of zinc is greater than 3 relative to calcium, zinc chloride produced during molding will be vinyl chloride. It may become a decomposition catalyst for resin, and sudden blackening and decomposition called “zinc burn” may occur.

  The addition amount of the Ca—Zn-based stabilizer is preferably 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin (A), and is 0.3 or more or 1.8. It is more preferable that the amount is not more than part by mass. When the addition amount of the Ca—Zn stabilizer is less than 0.1 parts by mass, the effect of imparting thermal stability may not be sufficient, while when the addition amount exceeds 2.0 parts by mass, “zinc It may cause sudden blackening and decomposition called “burning”.

  In order to impart antifogging properties to the food packaging film of the present invention, it is preferable to add an ester compound of a polyhydric alcohol and a fatty acid. Examples of the ester of polyhydric alcohol and fatty acid include monoglycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene alkyl ether. The monoglycerin fatty acid ester is preferably a monoglycerin ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include monoglycerol laurate, monoglycerol myristate, monoglycerol palmitate, monoglycerol stearate, monoglycerol oleate, and monoglycerol linoleate. As the polyglycerol fatty acid ester, a polyglycerol ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms is preferable. Specific examples include polyglycerol laurate, polyglycerol myristate, polyglycerol palmitate, polyglycerol stearate, polyglycerol oleate, and polyglycerol linoleate.

  The sorbitan fatty acid ester is preferably a sorbitan ester of a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. Specific examples include sorbitan laurate, sorbitan myristate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan linoleate, and the like. The polyoxyethylene alkyl ether is preferably a saturated alcohol polyoxyethylene alkyl ether having 12 to 18 carbon atoms, more preferably a polyoxyethylene alkyl ether having 3 to 7 added moles of ethylene oxide. . Specific examples include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene palmityl ether, and polyoxyethylene stearyl ether. These may be used alone or in combination of two or more.

  The addition amount of the polyhydric alcohol and fatty acid ester compound is preferably 0.1 to 5.0 parts by mass, more preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the vinyl chloride resin (A). Or it is more preferable that it is 4.5 mass parts or less, and it is still more preferable especially that it is 1.0 mass part or more or 3.5 mass parts or less among them. If the amount of the ester compound added is 0.5 parts by mass or more, sufficient antifogging properties can be exhibited. For example, when a food container or the like is packaged and stored, water droplets are generated on the film, and the contents are confirmed. It is possible to eliminate the problem of not being able to. On the other hand, if it is 5.0 parts by mass or less, excessive bleeding out of the polyhydric alcohol and fatty acid ester compound to the surface of the molded product can be suppressed, and the packaging suitability can be satisfied.

  Furthermore, to the extent that the effects of the present invention are not impaired, the present resin composition is heat stabilizer, antioxidant, ultraviolet absorber, light stabilizer, antibacterial / antifungal agent, antistatic agent, lubricant, pigment, Additives such as dyes can be blended.

  As a method for producing the food packaging film of the present invention, a known method can be used. For example, vinyl chloride resin (A), modified epoxidized vegetable oil (B), aliphatic dibasic acid ester compound (C), polyester compound (D), and other additives, V-type blender, ribbon blender , Mixing with a mixer such as a Henschel mixer, kneading it with a kneader such as an extruder, mixing roll, Banbury mixer, kneader, or combining and kneading the mixer and kneader Then, for example, a film can be manufactured by a T-die method or an inflation method.

  The film thus obtained has all of low elution (safety), packaging suitability (flexibility), and film appearance, and therefore can be widely used as a food packaging film.

  In general, "film" refers to a thin flat product that is extremely small compared to its length and width and whose maximum thickness is arbitrarily limited, and is usually supplied in the form of a roll (Japan) Industrial standard JISK6900), and in general, “sheet” refers to a product that is thin by definition in JIS and generally has a thickness that is small instead of length and width. However, since the boundary between the sheet and the film is not clear and it is not necessary to distinguish the two in terms of the present invention, in the present invention, even when the term “film” is used, the term “sheet” is included and the term “sheet” is used. In some cases, “film” is included.

  Examples are shown below, but the present invention is not limited by these. In addition, the various measured values and evaluation about the raw material and test piece which are displayed in this specification were performed as follows.

(1) Ratio of multimers in modified epoxidized vegetable oil Using gel permeation chromatography (column: trade name TSKgel G2000HXL of Tosoh Corporation), THF (solution concentration 2.5 mg / mL, solution injection amount 0) .05 mL, flow rate 1 mL / min, temperature 40 ° C.). From the obtained chart, the proportion of the monomer of the epoxidized vegetable oil was calculated, and the proportion of the multimer was determined by the following formula.
Multimer ratio (mass%) = 100 (mass%) − “monomer ratio (mass%)”

(2) Dissolution Based on the evaporation residue test method (single-sided method) defined in Ministry of Health and Welfare Notification No. 20, isooctane was used as a solvent, contact area with the solvent: 25 cm ² , solvent amount: 2 mL / cm ² , test temperature: 25 The elution amount with respect to isooctane was measured under the conditions of ° C and test time: 30 minutes, and the elution amount is shown in Table 1. If the elution amount is 120 ppm or less, it can be evaluated as “pass”.

(3) Flexibility (storage modulus (E '))
Using a dynamic viscoelasticity measuring device (product name: viscoelastic spectrometer DVA-200, manufactured by IT Measurement Co., Ltd.), vibration frequency: 10 Hz, temperature rising rate: 3 ° C./min, strain 0.1% The storage elastic modulus (E ′) was measured from −100 ° C. to 200 ° C., the storage elastic modulus (E ′) at 25 ° C. was read from the obtained data, and the value is shown in Table 1. If the storage elastic modulus (E ′) at 25 ° C. is 100 MPa to 500 MPa, it can be evaluated as “pass”.

(4) Film unwinding property (film unwinding force)
After winding 10 mm of the 50 mm wide film produced in the examples and comparative examples on a cylindrical paper tube having an outer diameter of 85 mm and a length of 330 mm, the outer diameter of 25 mm is placed in the paper tube so that the film roll rotates smoothly. A pipe made of vinyl chloride resin was inserted. Next, the load applied when the film was unwound at a speed of 3 cm / sec was measured using a force gauge while holding the film tip with a clip so that the film could be unwound uniformly. If the unwinding force at this time is 0.1 to 0.5 N / 50 mm, it can be evaluated as “pass”.
Incidentally, the film unwinding force is influenced by the amount and molecular weight of the plasticizer, or the type and amount of the antifogging agent, and particularly has a correlation with the blending amount of the low molecular weight plasticizer. If the blending amount is large, bleeding on the film surface increases and the unwinding force decreases.

(5) Film appearance change Films prepared in Examples and Comparative Examples were cut into a length of 50 mm and a width of 50 mm, and the obtained sample for evaluation was subjected to a low temperature / low humidity atmosphere of 0 ° C. and 15% RH, and 40 The sample is allowed to stand for 7 days in a high-temperature and high-humidity atmosphere at 80 ° C. and 80% RH. Table 1 shows the results of evaluation of “A” for those that did not change under both conditions (not whitened) and “B” for those that were whitened under any of the conditions.

The materials used in the following examples and comparative examples were prepared as follows.
[Vinyl chloride resin (A)]
(A) -1: Polyvinyl chloride (vinyl chloride homopolymer, average degree of polymerization 1050)

[Modified Epoxidized Vegetable Oil (B)]
(B) -1: Epoxidized soybean oil having a peroxide value of 13.3 (B) -2: Epoxidized soybean oil having a peroxide value of 15.1 (B) -3: Peroxide value of 10. Epoxidized soybean oil which is 1

[Aliphatic dibasic acid ester compound (C)]
(C) -1: Product name of Shin Nippon Rika Co., Ltd. Sansosizer DINA (Diisononyl adipate, weight average molecular weight: 398)
(C) -2: Trade name TOTM of J-Plus Co., Ltd. (trimellitic acid tris (2-ethylhexyl), weight molecular weight: 547)

[Polyester compound (D)]
(D) -1: Poly (1,3-butanediol / adipic acid) ester (weight average molecular weight: 6,000)
(D) -2: trade name of DIC Corporation Polylite OD-X-2044 (polyneopentyl adipate diol, weight average molecular weight: 6,800)
(D) -3: Trade name HS2P-103S of Toyokuni Oil Co., Ltd. (polypropylene sebacate diol, weight average molecular weight: 4,900)
(D) -4: Trade name D620 of JPLUS Co., Ltd. (dioctyl adipate / diisononyl adipate, weight average molecular weight: 2,800)
(D) -5: Sanyo Chemical Industries, Ltd. trade name Sanester 24625Y (poly (ethylene / butylene) adipate diol, weight average molecular weight: 11,300)

[Other ingredients (J)]
(J) -1: Product name ADK STAB SP-76 (Ca-Zn stabilizer) of Asahi Denka Kogyo Co., Ltd.
(J) -2: Succinic acid

Example 1:
(A) -1 is 100 parts by mass, (B) -1 is 15 parts by mass, (C) -1 is 25 parts by mass, (D) -1 is 10 parts by mass, and (J) -1 is 1 part by mass. After the mixture was added to the super mixer at a ratio, the temperature of the material was raised from room temperature to 130 ° C. while stirring, mixed with heating, and then taken out when cooled to 70 ° C. to obtain a resin composition.
The obtained resin composition was extrusion-molded at a resin temperature of 200 ° C. with a Φ40 mm single-screw extruder (L / D = 20) equipped with a T die (width 350 mm, gap 0.4 mm). A 01 mm film was obtained. About the obtained film, the ratio of the multimer in modified | denatured epoxidized vegetable oil, dissolution property, a softness | flexibility, film unwinding property, and the film external appearance change were evaluated. The results are shown in Table 1.

Example 2:
In Example 1, a film was produced in the same manner as in Example 1 except that (B) -1 was 20 parts by mass and (C) -1 was 20 parts by mass. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 3:
In Example 1, a film was produced in the same manner as in Example 1 except that (B) -1 was changed to 25 parts by mass and (C) -1 was changed to 15 parts by mass. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 4:
In Example 1, a film was produced in the same manner as in Example 1 except that (C) -1 was 20 parts by mass and (C) -1 was 15 parts by mass. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 5:
In Example 1, a film was produced in the same manner as in Example 1 except that (B) -1 was changed to 25 parts by mass and (C) -1 was changed to 20 parts by mass. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 6:
In Example 2, a film was produced in the same manner as in Example 1 except that (B) -2 was used instead of (B) -1. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 7:
In Example 2, a film was produced in the same manner as in Example 1 except that (D) -2 was used instead of (D) -1. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 8:
In Example 2, a film was produced in the same manner as in Example 1 except that (C) -2 was used instead of (C) -1. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 9:
In Example 2, a film was produced in the same manner as in Example 1 except that (D) -3 was used instead of (D) -1. The results of the same evaluation as in Example 1 are shown in Table 1.

Example 10:
In Example 2, except that (B) -3 was used instead of (B) -1, the proportion of the epoxidized vegetable oil multimer in the modified epoxidized vegetable oil (B) was changed to 7.8% by mass. Produced a film in the same manner as in Example 1. The results of the same evaluation as in Example 1 are shown in Table 1.

Comparative Example 1:
In Example 1, a film was produced in the same manner as in Example 1 except that (B) -1 was changed to 30 parts by mass and (C) -1 was changed to 10 parts by mass. The results of the same evaluation as in Example 1 are shown in Table 2.

Comparative Example 2:
In Example 1, a film was produced in the same manner as in Example 1 except that (B) -1 was changed to 10 parts by mass and (C) -1 was changed to 30 parts by mass. The results of the same evaluation as in Example 1 are shown in Table 2.

Comparative Example 3:
In Example 1, a film was produced in the same manner as in Example 1 except that (B) -1 was changed to 10 parts by mass and (C) -1 was changed to 15 parts by mass. The results of the same evaluation as in Example 1 are shown in Table 2.

Comparative Example 4:
A film was produced in the same manner as in Example 1 except that (B) -1 was 15 parts by mass, (C) -1 was 15 parts by mass, and (D) -1 was 20 parts by mass in Example 1. . The results of the same evaluation as in Example 1 are shown in Table 2.

Comparative Example 5:
Without blending the polyester compound (D), (A) -1 is 100 parts by mass, (B) -1 is 40 parts by mass, (C) -1 is 10 parts by mass, and (J) -1 is 1 mass. The mixture was put into a supermixer at a ratio of part, heated to a material temperature of 130 ° C. while stirring, mixed by heating, and then taken out when the material temperature was cooled to 60 ° C. to obtain a resin composition.
Using the obtained resin composition, a film was produced and evaluated in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 6:
In Example 2, 1.2 parts by mass of succinic acid (J) -2 was further added as a dicarboxylic acid, and a film was produced in the same manner as in Example 1. However, in the modified epoxidized vegetable oil contained in the film, Since the ratio of the multimer was excessive (58% by mass), the dispersion state of the modified epoxidized vegetable oil was poor, and a film having a good appearance could not be obtained. Therefore, the same evaluation as in Example 1 could not be performed.

Comparative Example 7:
In Example 2, a film was produced in the same manner as in Example 1 except that (D) -4 was used instead of (D) -1. The results of the same evaluation as in Example 1 are shown in Table 2.

Comparative Example 8:
In Example 2, a film was produced in the same manner as in Example 1 except that (D) -5 was used instead of (D) -1. However, since the polyester compound bleeded out on the film surface and a film having a good appearance could not be obtained, the same evaluation as in Example 1 could not be performed.

  The film of the present invention can be suitably used as, for example, a food packaging film.

Claims (5)

  A modified epoxidized vegetable oil (B) having a multimer content of 5 to 50% by mass relative to the vinyl chloride resin (A), an aliphatic having a weight average molecular weight of 200 to 1000 and a carbon number of 10 or less. A dibasic acid ester compound (C) and a polyester compound (D) having a weight average molecular weight of 3000 to 10,000 are blended, and (A) blending of a mixture of (B) and (C) with respect to 100 parts by mass The amount is 30 to 50 parts by mass, and the proportion of (B) in the mixture of (B) and (C) is 30 to 70% by mass, and (A) (D) relative to 100 parts by mass The film for food packaging characterized by the compounding quantity of 5-15 mass parts.   The film for food packaging according to claim 1, wherein the aliphatic dibasic acid ester compound (C) having 10 or less carbon atoms is diisononyl adipate.   The film for food packaging according to claim 1 or 2, wherein the polyester compound (D) is an adipic acid ester compound, a polyester polyol, or a mixture of an adipic acid ester compound and a polyester polyol.   The food packaging according to claim 3, wherein the adipic acid ester compound is a poly (1,3-butanediol / adipic acid) ester, a poly (1,4-butanediol / adipic acid) ester, or a mixture thereof. Film.   The film for food packaging according to claim 4, wherein the polyester-based compound (D) has a weight average molecular weight of 4000 to 9000.